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Abstract:

Damage indicating packaging is disclosed. A damage indicating material
may be applied between inner and outer wrapper layers. When the damage
indicating material is exposed to oxygen, excessive heat and/or excessive
pressure, the material changes in appearance to thereby alert the user
that the package may be compromised. The damage indicating material may
include an anti-counterfeiting taggant material. Active and intelligent
tamper-evident packaging is thus provided.

Claims:

1. A damage indicating package comprising: an inner wrapper layer
defining an interior volume structured and arranged to receive a product;
an outer layer at least partially covering the inner wrapper layer; and a
damage indicating material between the inner wrapper layer and the outer
wrapper layer.

2. The damage indicating package of claim 1, wherein the product is a
condom.

3. The damage indicating package of claim 1, wherein the product is a
food product or a pharmaceutical product.

18. A packaged product comprising: an inner wrapper layer defining an
interior volume containing the product; an outer layer at least partially
covering the inner wrapper layer; and a damage indicating material
between the inner wrapper layer and the outer wrapper layer.

19. The packaged product of claim 18, wherein the product is a condom.

20. The packaged product of claim 18, wherein the product is a food
product or a pharmaceutical product.

21. A method of making a damage indicating product package comprising
applying a damage indicating material to a layer of material that is
structured and arranged to receive a product therein.

22. A method of providing an indication that a product package has been
damaged comprising wrapping the product with at least one layer having a
damage indicating material applied thereto.

Description:

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. patent
application Ser. No. 14/272,156 filed May 7, 2014, which claims priority
from U.S. Provisional Patent Application Ser. No. 61/820,315 filed May 7,
2013 and U.S. Provisional Patent Application Ser. No. 61/971,187 filed
Mar. 27, 2014. This application also claims the benefit of U.S.
Provisional Patent Application Ser. No. 62/078,819 filed Nov. 12, 2014.
All of these applications are incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to damage indicating packaging for
condoms and other articles such as food products and pharmaceuticals.

BACKGROUND INFORMATION

[0003] Conventional condom packaging provides an expiration date, but no
obvious evidence of tampering. Air bubbles have been used in condom
packaging as an indication of whether the packaging has been compromised.
However, a need exists for an easy and reliable indication that condom
packages have been compromised. In addition, a need exists for other
types of damage indicating packaging for food products, pharmaceuticals
and the like.

SUMMARY OF THE INVENTION

[0004] An embodiment of the invention provides a damage indicating
material such as a reactive or responsive species in a formulation that
can be incorporated into a variety of substrates. The damage indicating
material may change color when exposed to oxygen, excessive heat and/or
excessive pressure. The damage indicating material may include an
anti-counterfeiting taggant material. One method of incorporating the
reactive/responsive material can involve printing a damage indicating ink
or coating on a substrate. One embodiment of the invention involves
printing a reactive/responsive ink formulation on plastic films used for
vacuum packaging. In one package style of this embodiment, the printed
vacuum packaging is used as a vacuum sealed overwrap around an
already-packaged product. Exemplary products include packaged condoms,
food and pharmaceuticals.

[0005] An aspect of the present invention is to provide a damage
indicating package comprising an inner wrapper layer defining an interior
volume structured and arranged to receive a product, an outer layer at
least partially covering the inner wrapper layer, and a damage indicating
material between the inner wrapper layer and the outer wrapper layer.

[0006] Another aspect of the present invention is to provide a damage
indicating packaging material comprising a film layer structured and
arranged for wrapping around a product, and a damage indicating material
applied to the film layer.

[0007] A further aspect of the present invention is to provide a packaged
product comprising an inner wrapper layer defining an interior volume
containing the product, an outer layer at least partially covering the
inner wrapper layer, and a damage indicating material between the inner
wrapper layer and the outer wrapper layer.

[0008] Another aspect of the present invention is to provide a method of
making a damage indicating product package comprising applying a damage
indicating material to a layer of material that is structured and
arranged to receive a product therein.

[0009] A further aspect of the present invention is to provide a method of
providing an indication that a product package has been damaged
comprising wrapping the product with at least one layer having a damage
indicating material applied thereto.

[0010] These and other aspects of the present invention will be more
apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG. 1 is a partially schematic front view of a sealed condom
package with a substantially transparent company logo and universally
recognized symbol in accordance with an embodiment of the invention.

[0012] FIG. 2 is a partially schematic back view of the sealed condom
package of FIG. 1 showing a substantially transparent universal throwaway
symbol in accordance with an embodiment of the invention.

[0013] FIG. 3 is a partially schematic front view of a condom package once
exposed to oxygen with tamper evident coloring displaying a universally
recognized symbol as a result of color bloom of a damage indicating
material in accordance with an embodiment of the present invention.

[0014] FIG. 4 is a partially schematic back view of the condom package of
FIG. 3 once exposed to oxygen with tamper evident coloring displaying a
universally recognized symbol or customized symbol as a result of the
color bloom of the damage indicating material in accordance with an
embodiment of the present invention.

[0015] FIG. 5 is the flow diagram illustrating a method of making a damage
indicating condom package in accordance with an embodiment of the
invention.

[0016] FIG. 6 is a partially schematic side sectional view showing a
portion of a condom packaging material in accordance with an embodiment
of the present invention.

[0017] FIG. 7 is a partially schematic side sectional view showing a
portion of a condom packaging material in accordance with another
embodiment of the present invention.

[0020] The following is a detailed description of exemplary embodiments to
illustrate the principles of the invention. The embodiments are provided
to illustrate aspects of the invention, but the invention is not limited
to any embodiment. The scope of the invention encompasses numerous
alternatives, modifications and equivalents. Numerous specific details
are set forth in the following description in order to provide a thorough
understanding of the invention. However, the invention may be practiced
according to the claims without some or all of these specific details.
For the purpose of clarity, technical material that is known in the
technical fields related to the invention has not been described in
detail so that the invention is not unnecessarily obscured.

[0021] An embodiment of the present invention provides active and
intelligent product packaging including information printed thereon that
allows anyone seeing it to know that the packaging has been compromised
and to discard the product if damaged. A damage indicating material may
be utilized that causes the packaging to change color when exposed to
oxygen, extreme heat and/or excessive pressure such as compression or
tension. The damage-indicating packaging gives the user clear indication
that the product contained therein has been compromised and can be
immediately discarded.

[0023] In certain embodiments, the damage indicating packaging may be
provided as an overwrap for a previously packaged product, such as an
overwrap for pre-packaged food or pharmaceutical products. For example,
pharmaceutical pills, tablets, capsules, liquids, etc. that are packaged
in bottles, blister wraps and the like may be overwrapped with the damage
indicating packaging. In other embodiments, the food, pharmaceutical or
other product may be directly wrapped with the damage indicating
packaging.

[0024] Further features of the invention provide for the information to be
printed on a front and/or back layer of the packaging. The information
may include any one or more of manufacturing information, artwork, text,
logos, slogans, insignia, instructions or the like.

[0025] An embodiment of the invention also provides a process for
manufacturing damage-indicating packaging with a film layer of plastic,
foil, paper or the like having a damage indicating material applied
thereto. The packaging film layer and damage indicating material may be
exposed to electromagnetic radiation, which renders the damage indicating
material substantially colorless. In certain embodiments, the damage
indicating material may be added to a layer of the packaging prior to the
product being inserted and the packaging being sealed. A sealing unit may
seal the package layers together around each product and dispense the
packaged products either individually or in strips. The sealing unit may
also print manufacturing information on the sealed packages.

[0026] Referring now to an embodiment of the invention in more detail, in
FIGS. 1 and 2, the combination of a condom and a package therefor is
schematically shown at 100. The combination comprises a package shown
generally at 110, and a rolled condom shown generally at 120. The package
comprises a front wrapper panel or layer 130 and a back wrapper panel or
layer 140. The front 130 and back 140 wrapper layers are sealed to one
another around their respective edges. Labeling is shown generally at
150. Package instructions are shown generally at 199. In the embodiment
shown, the instructions 199 state "Contains tamper evident technology. If
indicator on wrapper changes to dark blue color please discard product".
As shown in FIG. 1, a front outer layer 210 covers the front wrapper
layer 130. A damage indicating material is applied on the front outer
layer 210. As shown in FIG. 2, a back outer layer 220 covers the back
wrapper layer 140, and a damage indicating material is applied on the
back outer layer 220.

[0027] Still referring to FIGS. 1 and 2, universal symbols 190, 200 and a
company logo 180 are printed on the package with a damage indicating
material that includes a reactive dye such as methylene blue, alternative
oxygen sensitive reactive dye, or alternative damage indicating material
on package interiors, and processed to convert them to a colorless or
different colored form. When the reactive damage indicating material is
subsequently activated by exposure to oxygen, extreme heat, or excessive
pressure, such as compression or tension, it changes in appearance. For
example, the reactive damage indicating material changes color when
exposed to oxygen. The color change should be sufficiently stable such
that the color is visible for a sufficiently long time period. In certain
embodiments, the long-term stability may be for periods of days, weeks,
months or years.

[0028] FIGS. 3 and 4 schematically illustrate the condom package 100 in a
damage-indicating state in which the condom wrapper has been torn. The
universal symbols 390, 400 and company logo 380 are re-oxidized and
change color (in the case of methylene blue) due to exposure to oxygen,
or bloom with color due to extreme heat, excessive pressure, compression
or tension. Re-oxidation is indicated with a color bloom of the universal
symbols 390, 400 and company logo 380.

[0029] It will be understood that the rolled condom 120 as shown in FIGS.
1-4 has an open end 160 and a closed end 170. However, the precise
details of the condom 120 are not relevant to the present invention,
e.g., the condom may be pre-lubricated or not, may have a tip for
collection of ejaculate, etc.

[0030] FIG. 5 is a flow diagram illustrating a method of making a damage
evident condom package in accordance with an embodiment of the present
invention. In step 510, the interior wall of a condom packaging layer is
coated with a damage indicating material such as methylene blue, any
suitable alternative oxygen-sensitive reactive dyes, or responsive,
color-changing material combination. The material may be applied by any
suitable means such as spraying, brushing, screen printing, ink jet
printing or the like. Methylene blue dye may be used in the printing
process. Other responsive materials may be thiazines, thionines,
oxazines, azines, triphenylmethane, indophenol, indigo, thioindigo,
pyridinium viologens, and quinone-based species. Additional responsive
materials may be non-toxic phosphorous pigmentation, or any alternative
oxygen sensitive reactive dyes or any dyes that change color when exposed
to oxygen, extreme heat, or excessive pressure, compression or tension.
The responsive, damage indicating material may comprise more than one
type of reactive dye. There will be associative processes to prepare the
oxygen sensitive reactive dyes to reduce it to a colorless form. The
printer may be of conventional construction and operation and sprays dye
onto the packaging. The manufacturing information is provided by a
processor (not shown), the operation of which is not germane to this
invention, and which also controls printing by the sealing unit.

[0031] In step 520, another layer, which may also have damage indicating
material applied thereto, is sealed or otherwise attached to the layer
formed in step 510, e.g., to thereby form a pocket.

[0032] In step 530, a condom is inserted into the condom package or
pocket. The condom may optionally be pre-wrapped in any suitable type of
wrapper prior to insertion into the pocket. A company logo and/or
universal symbols may be printed on one or more of the layers of
packaging.

[0033] In step 540, a sealing unit seals the package layers together
around each condom 120 and dispenses the condoms either individually or
in strips.

[0034] In step 550, the sealed condom package is exposed to
electromagnetic radiation, such as ultraviolet radiation or any other
radiation of suitable wavelength, e.g., to render the damage indicating
material substantially colorless.

[0035] In step 560, the chemical compound is exposed to oxygen to change
the color of the damage indicating material by oxidation or another type
of chemical reaction that changes the reactive dye from colorless to
colored or from one color to another upon tampering, extreme heat,
excessive pressure, compression, tension or any other breach of the
condom wrapper such as a tear, pin-prick, or intentionally opening condom
packaging. Printing between the layers of packaging prevents the dye from
coming into contact with the condom. Is thus not possible for a user to
experience any reaction due to contact with the dye.

[0036] FIGS. 6 and 7 are partially schematic side sectional views
illustrating various condom packaging layers in accordance with
embodiments of the present invention. In FIG. 6, an outer layer 610 is
provided with a layer of damage indicating material 615 applied thereto.
An inner condom wrapper layer 630 is located adjacent to the outer layer
610 and damage indicating material 615. In certain embodiments, the inner
wrapper layer 630 may not be adhered to the layer of damage indicating
material 615, as shown by the gap 640 in FIG. 6. Although the gap 640 is
shown as a physical spacing between the layers 630 and 615 in FIG. 6, it
should be recognized that the gap may be closed such that the layers 630
and 615 contact each other. For example, when the space between the outer
layer 610 and inner wrapper layer 630 is evacuated, the layer of damage
indicating material 615 would typically contact the underlying inner
wrapper layer 630. Alternatively, when the space between the outer layer
610 and inner wrapper layer 630 is filled with an inert or non-reactive
gas, the pressure of the gas may result in the formation of a physical
gap 640, as shown in FIG. 6.

[0037] The embodiment shown in FIG. 7 is similar to the embodiment of FIG.
6, except the layer of damage indicating material 615 is applied to the
outer surface of the inner wrapper layer 630 rather than the inner
surface of the outer layer 610.

[0038] In accordance with embodiments of the present invention, the
various inner condom wrapper layers and outer layers may be made of any
suitable materials such as polymeric films, foils, paper and the like.
Some examples of polymeric layers include cellulosic materials, vinyl
polymers such as polyvinyl alcohol and polyacrylates, polyolefins such as
polyethylene, polyethylene terephthalate (PET), ethylene vinyl acetate
copolymers, polyethylene, nylon (polyamide) and the like. The inner
wrapper layers and outer layers may be made of the same or different
materials. In certain embodiments, the inner wrapper layers may comprise
foil coated with any of the aforementioned polymers, or such polymers
alone. In certain embodiments, the outer layers may comprise polyethylene
or the like, which may optionally be coextruded with nylon or the like.

[0039] In an embodiment of the invention, a condom or other product is
disposed in an inner wrapper, an outer wrapper surrounds the inner
wrapper, and a layer of damage indicating material is applied to the
inner surface of the outer wrapper. Alternatively, as described above,
the outer surface of the inner wrapper may have the damage indicating
material applied thereto. In both of these embodiments, the space between
the inner and outer wrappers may be evacuated by any suitable type of
vacuum source in order to remove gasses including oxygen from the space
between the wrappers. In this embodiment, when the outer wrapper is
punctured, torn or otherwise breached, air will fill the previously
evacuated space between the inner and outer wrappers, thereby coming into
contact with the relatively large surface areas of the wrappers, i.e.,
the outer surface of the inner wrapper will be exposed to air and the
inner surface of the outer wrapper will be exposed to air. The presence
of the damage indicating material on the inner surface of the outer
wrapper and/or on the outer surface of the inner wrapper will thereby
provide an indication that the outer wrapper has been punctured, torn or
otherwise breached and that air has entered the space between the
wrappers. As an alternative to evacuating the space between the inner and
outer wrappers, the inner space may be at least partially filled with an
inert or non-reactive gas such as nitrogen or the like that does not
cause the damage indicating material to react and change colors.

[0040] In accordance with an embodiment of the present invention,
dual-wrapper arrangements as described above may be made by providing a
pre-packaged condom or other product in the inner wrapper, followed by
applying the outer wrapper around the inner wrapper. For example, the
outer wrapper may be provided as a pre-formed pocket in which the inner
wrapper containing the product is inserted, followed by sealing of the
open end of the outer wrapper. As discussed above, before, during or
after the sealing operation, the space between the inner and outer
wrappers may be evacuated and/or filled with a non-reactive gas. As
another example, separate sheets of outer wrapper material may be placed
on opposite sides of the inner wrapper containing the product, following
by sealing of the peripheral edges of the outer wrapper layers together
to thereby seal the inner wrapper and product within the outer wrapper.
Again, the space between the inner and outer wrappers may be evacuated
and/or filled with a non-reactive gas during the sealing operation. Such
operations, in which the product is first sealed in the inner wrapper
followed by sealing an outer wrapper around the inner wrapper, may be
conducted contemporaneously with each other, e.g., the inner and outer
wrappers may be applied in the same manufacturing operation.
Alternatively, pre-packaged products may be modified by applying the
outer wrapper at a different time or location, e.g., at a different
facility from the original product manufacturing location.

[0041] In accordance with another embodiment of the present invention, a
single product wrapper is provided with multiple laminated layers in
which at least one of the layers contains the damage indicating material.
For example, a layer of damage indicating material may be sandwiched
between inner and outer polymeric layers to provide a composite wrapper
structure with damage indicating capabilities. As another example, a
layer of damage indicating material may be applied on the inner surface
of the single product wrapper. In this embodiment, the damage indicating
material layer would be exposed to the product, and the damage indicating
material must be non-reactive with the material of the product or any
other liquids or gasses contained within the wrapper, and the damage
indicating layer must not damage the product or vice versa.

[0042] The damage indicating material may comprise an absorption-based
species that produces a visible color change caused by chromogenic
chemistry that involves oxidation by molecular oxygen. Examples include
methylene blue, resorufin, resazurin, thiazine, thionines, oxazine,
azine, triphenylmethane, indophenol, indigo, thioindigo, pyridinium
viologen, and quinone-based species. The damage indicating material may
also comprise luminescence-based species such as polycyclic aromatic
hydrocarbons, polypyridyl complexes, metalloporphyrins, including
platinum and palladium complexes, cyclometallated complexes, and other
luminescent metal complexes such as lead, aluminum, copper, gold,
europium, terbium, molybdenum, and the like. Other damage indicating
material species include fullerenes, fluorescent polymers, and modified
polymeric materials containing absorption-based or luminescence-based
species described above. Additional responsive materials may be non-toxic
phosphorous pigmentation, or any alternative oxygen sensitive reactive
dyes or any dyes that change color when exposed to oxygen, extreme heat,
or excessive pressure, compression or tension.

[0043] The reactive/responsive species can be incorporated into a variety
of formulations including inks, gels, plastics, composites and the like
Ink formulations include resin/binder variations such as gelatin,
cellulosics such as hydroxyethylcellulose (HEC), ethyl cellulose,
cellulose acetate, polyvinylalcohol (PVA), polyvinylpyrolidone (PVP),
polyamides, polyurethanes, polyethylene oxide (PEO), poly acrylates such
as polymethyl methacrylate (PMMA), polymethacrylate, and polystyrene or
modified polystyrenes. The ink formulations may include inks typically
used on plastic films and vacuum packaging films, or for pad printing,
flexo printing, gravure printing, dot matrix style printing,
steganography printing, and the like. Semiconductor variations include
oxides of titanium, tin, tungsten, zinc and/or mixtures thereof.
Semiconductor size variations include submicron diameter, sub 50 nm
diameter, and sub 10 nm diameter. Sacrificial electron donor variations
may be a mild reducing agent, amine such as sodium salt of
ethylenediaminetetraacetic acid (NaEDTA) or triethanolamine (TEOA),
saccharide such as glucose or fructose, antioxidant such as ascorbic acid
or citric acid, or other easily oxidizable species such as glycerin or
oxidizable polymer such as polyvinylalcohol (PVA). Additive variations
include solubility modifiers such as surfactants, permeability modifiers
such as silicones, and modifiers for oxygen transmissibility rate (OTR)
or water vapor transmissibility rate (WVTR). Examples of additives
include moisture absorbers, oxygen scavengers, microwave susceptors and
antimicrobials.

[0044] In certain embodiments, anti-counterfeiting taggant materials may
be added to the formulations in order to authenticate the product in
order to protect against counterfeiting. Known types of taggants may be
added to the damage indicating material. For example, taggant particles
or compositions may be added to coatings, inks and adhesives, or embedded
in packaging layers and/or labels. Types of anti-counterfeiting taggant
materials include infrared (IR) responsive particles and inks,
ultraviolet (UV) responsive particles and inks, secure pigments,
metachromic materials, color-shift materials, thermochromic materials,
and the like. A non-limiting example of commercially available taggants
that may be added to, or used in association with, the damage indicating
materials of the present invention is a particulate taggant material sold
under the designation Microtaggant by Microtrace, LLC. Other types of
commercially available taggant materials include SunGuard inks sold by
Sun Chemical Corporation. When taggant particles or compositions are
added to the present damage indicating coatings, they may typically be
present in amounts ranging from a minimal detectable trace amount up to 5
or 10 weight percent of the coating, or more. For example, taggants may
comprise from 0.001 to 5 weight percent, or from 0.01 to 2 weight
percent, or from 0.1 to 1 weight percent of the material.

[0046] The damage indicating material may be printed or applied to a
packaging substrate by any suitable means such as spraying, screen
printing, brushing, immersion, ink jet printing, or the like. Various
printing variations may be used for the damage indicating inks, such as
variable coating thicknesses, and variable coating line widths. A micro
dot or dot matrix style to increase surface area of ink within overall
mark is illustrated in FIG. 12. A cross hatch style to increase surface
area of ink within overall mark is illustrated in FIG. 13.

[0047] The packaging in its completed form may have a company logo
displayed clear on one side and a clear icon of a trashcan on the reverse
side. If opened for intended use or accidentally or intentionally pricked
exposing the product inside, exposed to extreme heat, or excessive
compression or tension, the coloring of the packaging will change,
highlighting the company logo with universal "NO" symbols emblazoned over
it, including, but not limited to the symbols for "Do not Enter",
"Prohibited", an "X", a circle, square, triangle with a backslash or line
going through it, horizontally, vertically, or diagonally, a stop sign, a
hand, trash can or customized symbol. On the reverse side a trash can
icon or alternative customized symbol(s) will also color change
indicating that the packaging and the product contained within should be
thrown away. In certain embodiments, anti-counterfeiting indicia may be
printed or otherwise applied to the packaging and/or labels applied to
the packaging.

[0048] The disclosed embodiments are illustrative, not restrictive. While
specific configurations including a packaged condom have been described,
it is understood that the present invention can be applied to a wide
variety of other packaging for other types of products including paper,
foils, or plastics, as well as any combination thereof, such as
foil-lined paper, plastic-lined paper or a wax-lined paper. The package
may take a variety of forms such as rectangular, oval, etc., or can be
male or female condom packaging, or packaging for other types of
products. The package may be provided with a separation structure, such
as an edge tear area, a zipper-locked edge area, or an openable,
adhesively sealed edge area. There are many alternative ways of
implementing the invention. Alternative embodiments include transparent
or translucent plastic lids, transparent or translucent plastic
containers. Plastics can be LDPE, HDPE, PP, or a combination of plastics
including, but not limited to polycarbonates, or acrylics.

[0050] The following examples are intended to illustrate various aspects
of the present invention, and are not intended to limit the scope of the
invention.

EXAMPLE 1

[0051] A damage indicating material was made as follows. Ten grams of 5%
aqueous solution of hydroxyethylcellulose (HEC) and 2.5 grams of 5%
aqueous dispersion of titanium dioxide (TiO2) were added to a 20 mL
amber glass scintillation vial. The mixture was sonicated for
approximately 30 minutes in a warm ultrasonic bath. After dispersing the
TiO2, 0.5 grams of 5% aqueous solution of methylene blue (MB) was
added to the mixture. The mixture was sonicated or magnetically stirred
for 10-15 minutes to disperse the MB in the aqueous mixture. After
dispersing the MB into the mixture, 0.15 g of triethanolamine (TEOA) were
added using a plastic or glass pipet. The final formulation was sonicated
for approximately 30 minutes in a warm ultrasonic bath prior to substrate
application.

[0052] The formulation was applied as a thin layer of glass or plastic
film substrate and was allowed to dry. Standard laboratory glass
microscope slides and 3 mil thick co-extruded polyethylene-nylon vacuum
packaging film were used as substrates for coating. The plastic film was
also used as an overwrap to seal the coated glass slides or plastic film
prior to activation and deactivation. The formulation was typically
applied by painting a thin film on the substrate with a paint brush.
Uniform film casting can also be accomplished using a spin coater or K
bar techniques. The coated substrates were allowed to dry within a dark
oven set at 50° C. for 16 hours. The resultant blue layer had a
dry-film thickness of approximately 2 mils or less with variations in
thickness dependent on the exact formulation. The dried, blue films of
damage indicating material were vacuum sealed within a plastic film
overwrap. Following evacuation and thermal sealing, the material was
"activated" under a UV lamp to convert the blue MB form to a white leuco
MB form. Upon such UV exposure, the layer changed from substantially blue
to off-white or light gray. After activation, the layer was exposed to
air by puncturing or cutting open the vacuum overwrap, resulting in a
change back to the blue color. After the color transformation, the layer
retained a significant degree of its blue color for over several weeks.

[0053] The formulations in Examples 2 through 8 used commercial ink
formulations for flexo and gravure printing by Siegwerks (Ink 4 and Ink
6) Ink 6 was also modified for this work to give Ink 6A with no water,
ink 6B with no water or titanium dioxide, ink 6C with no water and nano
titanium oxide and ink 6D with no water and additives to increase oxygen
permeability. Thus, the six different starting ink formulations are Ink
4, 6, 6A, 6B, 6C and 6D. Modifications to the starting ink formulations
yield reactive/responsive, damage indicating materials. The
Reactive/responsive, damage indicating materials are labeled as Ink X-Y
where X=4, 6A, 6B, 6C, 6D and Y=A through J.

[0054] A reactive/responsive ink formulation was made as follows. Two
grams of well mixed ink formulation (Ink 4, 6A, 6B, 6C or 6D) were added
to a 20 mL amber glass scintillation vial. Then 0.01-0.02 grams of the
reactive/responsive species (methylene blue=MB) was weighed into the
vial. Finally 0.10-0.80 grams of a sacrificial electron donor (TEOA) was
weighed into the vial. A magnetic stir bar was added to the vial and the
mixture was stirred and/or ultrasonicated until the dye was well
dissolved or dispersed (half hour to 24 hours).

[0055] Prior to printing, the substrate was dried to remove any residual
moisture. The substrate was a 75 micron thick, 2 layer co-extruded film
composed of nylon and polyethylene. A small amount of the
reactive/responsive ink formulation was applied to the dried substrate. A
K-Bar (#0, #2 or #6) was used to achieve a uniform film thickness. The
ink was drawn down with the K-Bar using steady, constant pressure and
speed. The printed substrate was dried in a 50 degree Celsius oven until
the ink set (1 hour to 24 hours). The dried printed substrate was
evacuated and heat sealed using a commercial vacuum sealer. In one
package style of this embodiment, the dried printed substrate is used as
a vacuum sealed overwrap around an already-packaged product such as a
packaged condom.

[0056] The reactive/responsive ink formulation on the dried, printed and
vacuum-sealed substrate was activated with UV light. The UV lamp was
allowed to warm up for at least 1 hour so that the UV intensity was
stable and consistent. The ink was UV activated by exposing the printed
and sealed substrate at a set distance (3 inches) and intensity
(˜10 mW/cm2 with 1 hour warm up) to achieve a stable color change.
The MB changes from blue to the colorless leuco form. After activation,
the layer was exposed to air by puncturing or cutting open the
vacuum-sealed overwrap. Color change was monitored over the course of
approximately 20 minutes. The color started to change with the first
minute after exposure.

EXAMPLE 2

[0057] Reactive/responsive, damage indicating materials were made using
Ink 6 with methylene blue (MB) as the reactive/responsive species and
triethanolamine (TEOA) as the sacrificial electron donor as set forth in
Table 1. Quantities are in grams. The damage indicating material was made
as follows. Two grams of well mixed Ink 6 were added to a 20 mL amber
glass scintillation vial. Then 0.01-0.02 grams of the reactive/responsive
species (methylene blue=MB) was weighed into the vial. Finally 0.10-0.80
grams of a sacrificial electron donor (TEOA) was weighed into the vial. A
magnetic stir bar was added to the vial and the mixture was stirred
and/or ultrasonicated until the dye was well dissolved or dispersed (half
hour to 24 hours).

[0058] Prior to printing, the substrate was dried to remove any residual
moisture. The substrate was a 75 micron thick, 2 layer co-extruded film
composed of nylon and polyethylene. A small amount of the
reactive/responsive ink formulation was applied to the dried substrate. A
K-Bar (#0, #2 or #6) was used to achieve a uniform film thickness. The
ink was drawn down with the K-Bar using steady, constant pressure and
speed. The printed substrate was dried in a 50 degree Celsius oven until
the ink set (1 hour to 24 hours). The dried printed substrate was
evacuated and heat sealed using a commercial vacuum sealer. In one
package style of this embodiment, the dried printed substrate is used as
a vacuum sealed overwrap around an already-packaged product such as a
packaged condom.

[0059] The damage indicating material was activated on the dried, printed
and vacuum-sealed substrate with UV light. The UV lamp was allowed to
warm up for at least 1 hour so that the UV intensity was stable and
consistent. The ink was UV activated by exposing the printed and sealed
substrate at a set distance (3 inches) and intensity (˜10 mW/cm2
with 1 hour warm up) to achieve a stable color change. The MB changes
from blue to the colorless leuco form. After activation, the layer was
exposed to air by puncturing or cutting open the vacuum-sealed overwrap.
Color change was monitored over the course of approximately 20 minutes.
The color started to change with the first minute after exposure.

[0060] Reactive/responsive, damage indicating materials were made using
Ink 6 with methylene blue (MB) as the reactive/responsive species and
glycerol as the sacrificial electron donor as set forth in Table 2.
Quantities are in grams. The damage indicating material was made as
described in Example 2.

[0061] Reactive/responsive, damage indicating materials were made using
Ink 6 with resorufin (RR) as the reactive/responsive species and
triethanolamine (TEOA) as the sacrificial electron donor as set forth in
Table 3. Quantities are in grams. The damage indicating material was made
as described in Example 2.

[0062] Reactive/responsive, damage indicating materials were made using
Ink 4 with resorufin (RR) as the reactive/responsive species and
triethanolamine (TEOA) as the sacrificial electron donor as set forth in
Table 4. Quantities are in grams. The damage indicating material was made
as described in Example 2.

[0063] Reactive/responsive, damage indicating materials were made using
Ink 6A, 6C and 6D with methylene blue (MB) as the reactive/responsive
species and triethanolamine (TEOA) as the sacrificial electron donor as
set forth in Table 5. Quantities are in grams. The damage indicating
material was made as described in Example 2.

[0064] Reactive/responsive, damage indicating materials were made using
Ink 6A and 6D with resorufin (RR) as the reactive/responsive species and
triethanolamine (TEOA) as the sacrificial electron donor as set forth in
Table 6. Quantities are in grams. The damage indicating material was made
as described in Example 2.

[0065] Reactive/responsive, damage indicating materials were made using
Ink 6C with resorufin (RR) as the reactive/responsive species and
triethanolamine (TEOA) as the sacrificial electron donor as set forth in
Table 7. Response was modulated with dilute acetic acid and dilute
ammonium hydroxide. Quantities are in grams. The damage indicating
material was made as described in Example 2.

[0071] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to those
skilled in the art that numerous variations of the details of the present
invention may be made without departing from the invention.

[0072] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to those
skilled in the art that numerous variations of the details of the present
invention may be made without departing from the invention as defined in
the appended claims.